EP1862442B1 - Procede d oxydation de composants organiques - Google Patents

Procede d oxydation de composants organiques Download PDF

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EP1862442B1
EP1862442B1 EP06714279.4A EP06714279A EP1862442B1 EP 1862442 B1 EP1862442 B1 EP 1862442B1 EP 06714279 A EP06714279 A EP 06714279A EP 1862442 B1 EP1862442 B1 EP 1862442B1
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catalyst
reaction
group
represented
formula
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EP1862442A1 (fr
EP1862442A4 (fr
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Y. Res. Center Daicel Chemical Ind. Ltd Kajikawa
N. Res. Center Daicel Chemical Ind. Ltd. Hirai
J. Res. Center Daicel Chemical Ind. Ltd Kuwana
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
    • C07C27/12—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
    • C07C35/06—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
    • C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to oxidation methods of organic compounds, and production processes of organic compounds. More specifically, it relates to oxidation methods and production processes of organic compounds by the catalysis of imide compounds, which can reduce cost for making up for losses of the catalysts denaturated in the reaction.
  • Imide compounds such as N-hydroxyimide compounds, N-alkoxyimide compounds, and N-acyloxyimide compounds are known to act as very excellent catalysts in oxidation of organic compounds using molecular oxygen, since they show high reaction efficiencies and high selectivities and can be applied to a wide variety of substrates in the oxidation (e.g., Patent Documents 1, 2 and 3).
  • these imide compounds undergo denaturation and thereby gradually decrease in activity in reaction. The denaturation may occur through several processes, and main possible factors thereof are as follows.
  • the imide compounds change into N-hydroxyimides before they develop activities in the reaction.
  • a possible mechanism for developing the activity is as follows. Initially, oxygen atom and hydrogen atom of the hydroxyl group adjacent to the nitrogen atom of imide easily undergo homogenous dissociation to form a radical. The formed radical withdraws hydrogen from a substrate to be oxidized to initiate a radical chain of oxidation reaction. The catalyst imide compound returns to its original configuration, repeats the same operation, and elongates the radical chain.
  • the radical formed from the N-hydroxyimide inevitably induces, due to its own nature, a "termination reaction" in which the radical is bound typically to a radical formed from the substrate to be oxidized. As a result, the N-hydroxyimide structure serving as an active site of the N-hydroxyimide is lost. The resulting compound derived from N-hydroxyimide and formed in the termination reaction further undergoes denaturation without returning to the N-hydroxyimide.
  • the imide moieties of imide compounds may be hydrolyzed by water formed in oxidation reactions and thereby undergo denaturation.
  • N-O bond (nitrogen-oxygen bond) of imide compounds may be cleaved typically by the action of a coexistent metal promoter (co-catalyst).
  • Patent Documents 4 and 5 each disclose a technique of recovering a denatured product (decomposed product) of a N-hydroxyimide compound, subjecting the same to a certain treatment according to necessity, reacting the treated product with hydroxylamine to reconstruct a N-hydroxyimide structure as an active site to thereby regenerate the N-hydroxyimide compound, and using the regenerated compound in oxidation.
  • This technique is economically advantageous as compared with the cases where a fresh N-hydroxyimide compound is purchased or the compound is produced after purchasing materials for the compound.
  • isolation of denaturated N-hydroxyimide compounds requires much energy, since the amounts of such N-hydroxyimide compounds used in oxidation of organic compounds with molecular oxygen are generally very small. Additionally, it is difficult to fully make up for losses due to denaturation by regenerating the catalysts from the isolated N-hydroxyimide compounds.
  • EP 1 151 791 discloses a method for separating a N-hydroxyimide oxidation catalyst from a reaction mixture.
  • an object of the present invention is to provide a method for oxidizing an organic compound and a process for producing an organic compound, which can easily, conveniently, and inexpensively make up for a loss of a catalyst denaturated in the course of an oxidation reaction of an organic compound with oxygen in the presence of a catalyst containing a N-hydroxyimide compound or N-(substituted oxy)-imide compound (a compound having a substituent on oxygen atom bound to the nitrogen atom of imide).
  • the present inventors After intensive investigations to achieve the object, the present inventors have found that the loss of a catalyst can be easily, conveniently, and inexpensively made up for by using, as the catalyst, one derivable from a reaction product, a reaction intermediate and/or a reaction byproduct, producing the catalyst using the target product, reaction intermediate and/or reaction byproduct, and supplying the produced catalyst to the reaction system, so as to make up for a loss of the catalyst denaturated in the course of reaction.
  • the present invention has been achieved based on these findings.
  • the present invention provides a method for oxidizing an organic compound with oxygen in the presence of a catalyst, in which the catalyst contains at least one N-hydroxy- or N-(substituted oxy)-imide compound derivable from at least one selected from the group consisting of a target product, a reaction intermediate, and a reaction byproduct, and the method includes the steps of producing the catalyst from at least one component selected from the group consisting of the target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction, and using the produced catalyst in the oxidation reaction so as to make up for a loss of the catalyst due to denaturation in the reaction.
  • Cyclic N-hydroxy- or N-(substituted oxy)-imide compounds are preferred as the N-hydroxy- or N-(substituted oxy)-imide compound.
  • an undenaturated catalyst can be recovered from the reaction mixture and used in the oxidation reaction, in addition to the catalyst produced from at least one component selected from the group consisting of a target product, a reaction intermediate, and a reaction byproduct each formed as a result of the reaction.
  • the at least one component selected from the group consisting of the target product, reaction intermediate, and reaction byproduct is preferably at least one of polycarboxylic acids, polycarboxylic acid anhydrides, and mixtures of them.
  • the oxidation method of an organic compound according to claim 1 is a method for oxidizing a cycloalkane represented by following Formula (1): wherein "n” represents an integer of 4 to 20, and the ring shown in the formula may be substituted, with oxygen to thereby yield at least one selected from the group consisting of corresponding cycloalkanones, corresponding cycloalkanols, and corresponding dicarboxylic acids having carbon atoms in the number of "n” in principal chain, in which the catalyst contains at least one cyclic N-hydroxy- or N-(substituted oxy)-imide compound derivable from at least one selected from the group consisting of a target product, a reaction intermediate, and a reaction byproduct and represented by following Formula (2) : wherein "m” represents an integer of 2 to (n-2) ; and R represents hydrogen atom or an organic group, and wherein the ring shown in the formula may be substituted, and the method includes the steps of producing the catalyst from at least one component selected from the group consist
  • the method of claim 1 includes, a method for oxidizing cyclohexane with oxygen to thereby yield at least one selected from the group consisting of cyclohexanone, cyclohexanol, and adipic acid, in which the catalyst contains at least one selected from the group consisting of N-hydroxy- or N-(substituted oxy)-succinimide and N-hydroxy- or N- (substituted oxy)-glutarimide derived from succinic acid and glutaric acid, respectively, each as a reaction byproduct, and the method includes the steps of producing the catalyst from succinic acid and/or glutaric acid formed as a result of the reaction, and using the produced catalyst in the oxidation reaction so as make up for a loss of the catalyst due to denaturation in the reaction; (ii) an embodiment for oxidizing cyclopentane with oxygen to thereby yield at least one selected from the group consisting of cyclopentanone, cyclopentanol, and glut
  • the oxidation method of an organic compound according to claim 1 is a method for oxidizing a compound represented by following Formula (3): wherein R a and R b are the same as or different from each other and each represent a group convertible into carboxyl group upon oxidation; R 1 , R 2 , R 3 , and R 4 are the same as or different from one another and each represent hydrogen atom, a halogen atom, or an organic group, where two or more of R a , R b , R 1 , R 2 , R 3 , and R 4 may be combined to form an aromatic or nonaromatic ring together with one or more carbon atoms constituting the benzene ring, with oxygen to thereby yield at least one selected from the group consisting of an aromatic dicarboxylic acid represented by following Formula (4a) and an aromatic dicarboxylic acid anhydride represented by following Formula (4b) : wherein R 1 , R 2 , R 3 , and R 4 are the same as or different from one another and each represent hydrogen
  • the catalyst can be produced from at least one component selected from the group consisting of the aromatic dicarboxylic acid represented by Formula (4a) and the aromatic dicarboxylic acid anhydride represented by Formula (4b) each formed as a result of the reaction and the produced catalyst can be used in the oxidation reaction.
  • the oxidation method of an organic compound according to claim 1 is a method for oxidizing a compound represented by following Formula (6): wherein R c , R d , and R e are the same as or different from one another and each represent a group convertible into carboxyl group upon oxidation; and R 5 , R 6 , and R 7 are the same as or different from one another and each represent hydrogen atom, a halogen atom, or an organic group, where two or more of R c , R d , R e , R 5 , R 6 , and R 7 may be combined to form an aromatic or nonaromatic ring together with one or more carbon atoms constituting the benzene ring, with oxygen to thereby yield at least one of an aromatic tricarboxylic acid represented by following Formula (7a) and an aromatic tricarboxylic acid monoanhydride represented by following Formula (7b): wherein R 5 , R 6 , and R 7 are the same as or different from one another and each represent hydrogen atom
  • the catalyst is preferably produced from at least one component selected from the group consisting of an aromatic tricarboxylic acid represented by Formula (7a) and an aromatic tricarboxylic acid monoanhydride represented by Formula (7b) each formed as a result of the reaction and the produced catalyst is preferably used in the oxidation reaction.
  • the oxidation method of an organic compound according to claim 1 is a method for oxidizing a compound represented by following Formula (9): wherein R f , R g , R h , and R i are the same as or different from one another and each represent a group convertible into carboxyl group upon oxidation; and R 8 and R 9 are the same as or different from each other and each represent hydrogen atom, a halogen atom, or an organic group, where two or more of R f , R g , R h , R i , R 8 , and R 9 may be combined to form a nonaromatic ring together with one or more carbon atoms constituting the benzene ring, with oxygen to thereby yield at least one selected from the group consisting of an aromatic tetracarboxylic acid represented by following Formula (10a), an aromatic tetracarboxylic acid monoanhydride represented by following Formula (10b), and an aromatic tetracarboxylic acid dianhydride represented by following Formula (10
  • the catalyst is preferably produced from at least one component selected from the group consisting of the aromatic tetracarboxylic acid represented by Formula (10a), the aromatic tetracarboxylic acid monoanhydride represented by Formula (10b), and the aromatic tetracarboxylic acid dianhydride represented by Formula (10c), each formed as a result of the reaction, and the produced catalyst is preferably used in the oxidation reaction.
  • the present invention provides a process for producing an organic compound, which process includes the steps of (A) oxidizing an organic compound with oxygen by the catalysis of at least one N-hydroxy- or N-(substituted oxy)-imide compound derivable from at least one selected from the group consisting of a target product, a reaction intermediate, and a reaction byproduct, (B) separating the target product formed in Step A from at least one component selected from the group consisting of a target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction and being to be used for producing the catalyst so as to make up for a loss of the catalyst due to denaturation in the reaction, (C) producing a catalyst using the at least one component separated in Step B, and (D) supplying the catalyst produced in Step C to Step A.
  • the production process can further include the step of (E) recovering an undenaturated catalyst from a reaction mixture and recycling the recovered undenaturated catalyst to Step A.
  • catalysts derivable from at least one selected from the group consisting of a target product, a reaction intermediate, and a reaction byproduct catalyst are used, and the catalysts are produced from at least one component selected from the target product, reaction intermediate and reaction byproduct each formed as a result of the reaction, and the produced catalysts are used in the oxidation reaction so as to make up for losses of the catalysts denaturated in the course of reaction.
  • target products must be separated from the reaction mixture somehow so as to yield products.
  • reaction intermediates must be separated so as to return to the reaction system, and reaction byproducts must be separated so as to be wasted. This separation step is an essentially necessary step regardless of whether or not they are supplied to the production of catalyst imide compounds.
  • the amounts of these components are generally larger than those of catalysts. Accordingly, losses of the catalysts due to denaturation can be very easily made up for, since the catalysts can be produced using only part of the target product, reaction intermediate, and/or reaction byproduct each formed as a result of the reaction. In addition, there is no need of isolating denaturated catalysts alone which exist in trace amounts. Accordingly, the present invention can easily, conveniently, and inexpensively make up for a loss of a catalyst N-hydroxy- or N-(substituted oxy)-imide compound denaturated in the course of oxidation of organic compounds with oxygen in the presence of the catalyst.
  • Organic compounds for use in the present invention as raw materials are not specifically limited, as long as they are such organic compounds that at least one N-hydroxy- or N- (substituted oxy) -imide compound such as a cyclic N-hydroxy-or N-(substituted oxy)-imide compound can be induced from at least one of target products, reaction intermediates (reaction intermediates derived from raw materials), and reaction byproducts (reaction byproducts derived from raw materials), each formed upon oxidation with oxygen.
  • N-hydroxy- or N-(substituted oxy)-imide compounds such as cyclic N-hydroxy- or N-(substituted oxy)-imide compounds are used as catalysts.
  • organic compounds used as the raw materials include the compounds represented by Formula (1), the compounds represented by Formula (3), the compounds represented by Formula (6), and the compounds represented by Formula (9).
  • n represents an integer of 4 to 20.
  • the ring shown of Formula (1) may have one or more substituents.
  • the repetition number "n” is preferably an integer of 5 to 15 and more preferably 5, 6, 12 or 15.
  • Protecting groups conventionally used in organic synthesis can be used herein.
  • the halogen atoms include fluorine atom, chlorine atom, bromine atom, and iodine atom.
  • alkyl groups which may have one or more halogen atoms include alkyl groups each having about one to about fifteen carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, and hexyl groups, of which alkyl groups having about one to about ten carbon atoms are preferred, and alkyl groups having about one to about six carbon atoms are more preferred; and haloalkyl groups having about one to about fifteen carbon atoms, such as trifluoromethyl and pentafluoroethyl groups, of which haloalkyl groups having about one to about ten carbon atoms are preferred, and haloalkyl groups having about one to about six carbon atoms are more preferred.
  • the cycloalkyl groups include, for example, cycloalkyl groups having about three to about fifteen members, such as cyclopentyl group and cyclohexyl group.
  • Examples of the aryl groups are phenyl and naphthyl groups.
  • the alkoxy groups which may have one or more halogen atoms include, for example, alkoxy groups having about one to about fifteen carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butyloxy, and hexyloxy groups, of which alkoxy groups having about one to about ten carbon atoms are preferred, and alkoxy groups having about one to about six carbon atoms are more preferred; and haloalkoxy groups having about one to about fifteen carbon atoms, such as trifluoromethoxy group, of which haloalkoxy groups having about one to about ten carbon atoms are preferred, and haloalkoxy groups having about one to about six carbon atoms are more preferred.
  • hydroxy (halo) alkyl groups examples include hydroxymethyl, hydroxyethyl, hydroxypropyl, 1-hydroxy-1-methylethyl, and 2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl groups, of which hydroxyalkyl groups having about one to about four carbon atoms and hydroxy-(haloalkyl) groups having about one to about four carbon atoms are preferred.
  • the acyl groups include aliphatic acyl groups having about one to about six carbon atoms, such as formyl, acetyl, propionyl, butyryl, isobutyryl, and pivaloyl groups; acetoacetyl group; and aromatic acyl groups such as benzoyl group.
  • compounds represented by Formula (1) compounds having no substituent on the cycloalkane ring (cycloalkanes), and compounds having one or more alkyl groups having one to six carbon atoms, such as methyl group, on the cycloalkane ring are preferred.
  • Representative examples of the compounds represented by Formula (1) are cyclohexane, cyclopentane, cyclododecane, and cyclopentadecane.
  • Oxidation of compounds represented by Formula (1) with oxygen by the catalysis of a N-hydroxy- or N-(substituted oxy)-imide compound yields corresponding cycloalkanones, cycloalkanols, and/or dicarboxylic acids having carbon atoms in the number of "n" in principal chain as main products.
  • the proportions of these products can be controlled by appropriately setting the reaction conditions such as type and amount of the catalyst, reaction temperature, and reaction time.
  • the reaction also yields, as byproducts, dicarboxylic acids having carbon atoms in a number of less than "n" in principal chain.
  • cyclohexane for example, is used as the compound represented by Formula (1)
  • cyclohexanone, cyclohexanol, or adipic acid, or a mixture of them is mainly produced, and succinic acid and/or glutaric acid, for example, is by-produced.
  • succinic acid and/or glutaric acid for example, is by-produced.
  • cyclopentane is used as the compound represented by Formula (1)
  • cyclopentanone, cyclopentanol or glutaric acid, or a mixture of them is mainly produced
  • succinic acid for example, is by-produced.
  • cyclododecane When cyclododecane is used as the compound represented by Formula (1), cyclododecanone, cyclododecanol, or dodecanedioic acid, or a mixture of them is mainly produced, and succinic acid and/or glutaric acid, for example, is by-produced.
  • the cyclic N-hydroxy- or N-(substituted oxy)-imide compound represented by Formula (2) and derivable from at least one selected from the group consisting of a target product, a reaction intermediate, and a reaction byproduct is used as the catalyst, and the catalyst is produced from at least one component selected from the group consisting of the target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction and the produced catalyst is used in the oxidation reaction so as make up for a loss of the catalyst due to denaturation in the reaction.
  • R represents hydrogen atom or an organic group.
  • the organic group in R is preferably a group that can be converted into hydrogen atom under reaction conditions upon, for example, hydrolysis.
  • organic groups include alkyl groups including alkyl groups having about one to about four carbon atoms, such as methyl and t-butyl groups, alkenyl groups such as allyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as 2,4-dinitrophenyl group, aralkyl groups such as benzyl, 2,6-dichlorobenzyl, and triphenylmethyl groups; groups that can form acetal or hemiacetal group with an adjacent oxygen atom, including substituted methyl groups such as methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxy methyl, and 2-methoxyethoxymethyl groups, substituted ethyl groups such as 1-ethoxyethyl, 1-methyl-1-methoxyethyl, and 2-methoxyethyl groups; tetrahydropyranyl group, tetrahydrofuranyl group, 1-hydroxyalkyl groups such
  • R examples include hydrogen atom; groups that can form acetal or hemiacetal group with an adjacent oxygen atom; groups that can be easily converted into hydrogen atom upon hydrolysis, including groups corresponding to an acid such as carboxylic acid, sulfonic acid, carbonic acid, carbamic acid, sulfuric acid, phosphoric acid, or boric acid, except that OH group is removed therefrom, such as acyl groups, sulfonyl groups, alkoxycarbonyl groups, and carbamoyl groups.
  • R is especialy preferably represents hydrogen atom or an acyl group. Of such acyl groups, aliphatic acyl groups having about one to about twenty carbon atoms are preferred, and aliphatic acyl groups having about one to about six carbon atoms are more preferred.
  • the ring shown of Formula (2) may have one or more substituents.
  • the substituents herein are as the substituents which the ring shown of Formula (1) may have.
  • cyclic imide compounds represented by Formula (2) are compounds derivable from succinic acid, including N-hydroxysuccinimide and N- (substituted oxy) succinimides such as N-acetoxysuccinimide; and compounds derivable from glutaric acid, including N-hydroxyglutarimide and N- (substituted oxy) glutarimides such as N-acetoxyglutarimide.
  • succinic acid including N-hydroxysuccinimide and N- (substituted oxy) succinimides such as N-acetoxysuccinimide
  • glutaric acid including N-hydroxyglutarimide and N- (substituted oxy) glutarimides such as N-acetoxyglutarimide.
  • cycloalkanes such as cyclohexane, cyclopentane, and cyclododecane are used as a raw material.
  • the target product, reaction intermediate, and/or reaction byproduct each formed as a result of the reaction and is used for the production of catalyst can be any of dicarboxylic acids having carbon atoms in the number of "n” in principal chain corresponding to the compound of Formula (1) used as the raw material (main products); and dicarboxylic acids having carbon atoms in a number less than "n" (byproducts).
  • succinic acid and/or glutaric acid is preferred as the raw material for the catalyst, when, of the compounds represented by Formula (1), cycloalkanes such as cyclohexane, cyclopentane, and cyclododecane are used as the raw material.
  • cycloalkanes such as cyclohexane, cyclopentane, and cyclododecane are used as the raw material.
  • R a and R b are the same as or different from one another and each represent a group convertible into carboxyl group upon oxidation.
  • the group convertible into carboxyl group upon oxidation include organic groups having a carbon-hydrogen bond at the benzyl position of the aromatic ring, such as alkyl groups, lower-order oxidized groups derived from alkyl groups (lower-order oxidized groups corresponding to alkyl groups, except with a carbon atom at the 1-position of alkyl groups being not oxidized to carboxyl group or an equivalent thereof), and cycloalkyl groups.
  • the alkyl groups include primary or secondary alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, and decyl groups.
  • alkyl groups having about one to about four carbon atoms are preferred, of which alkyl groups having about one to about three carbon atoms, such as methyl group, ethyl group, and isopropyl group, are especially preferred.
  • the lower-order oxidized groups derived from alkyl groups include hydroxyalkyl groups, formyl group, formylalkyl groups, and alkyl groups having oxo group.
  • the hydroxyalkyl groups include hydroxy-alkyl groups having about one to about six carbon atoms, such as hydroxymethyl, 1-hydroxyethyl, 1-hydroxypropyl, 1-hydroxy-1-methylethyl, and 1-hydroxybutyl groups.
  • Examples of the formylalkyl groups include formyl-(C 1 -C 6 alkyl) groups such as formylmethyl, 1-formylethyl, and 1-formylpropyl groups.
  • alkyl groups having oxo group examples include aliphatic acyl groups including aliphatic acyl groups having about one to about six carbon atoms, such as acetyl, propionyl, butyryl, pentanoyl, and hexanoyl groups. Among them, lower-order oxidized groups corresponding to alkyl groups having about one to about four carbon atoms are preferred, and those corresponding to alkyl groups having about one to about three carbon atoms are more preferred.
  • the cycloalkyl groups are cyclopentyl group and cyclohexyl group.
  • alkyl groups, lower-order oxidized groups thereof, and cycloalkyl groups may each have one or more substituents within ranges not adversely affecting the reaction.
  • substituents R a and R b methyl group is typically preferred.
  • R 1 , R 2 , R 3 , and R 4 are the same as or different from one another and each represent hydrogen atom, a halogen atom, or an organic group.
  • the halogen atom are fluorine atom, chlorine atom, and bromine atom.
  • the organic group can be any group that does not adversely affect the oxidation reaction and includes, for example, halogen atoms, alkyl groups which may have one or more halogen atoms, phenyl group, protected or unprotected hydroxyl group, and alkoxy groups which may have one or more halogen atoms.
  • halogen atoms, alkyl groups which may have one or more halogen atom, protected or unprotected hydroxyl group, and alkoxy groups which may have one or more halogen atoms can be the same as the substituents which the ring shown of Formula (1) may have.
  • R a , R b , R 1 , R 2 , R 3 , and R 4 may be combined to form an aromatic or nonaromatic ring together with one or more carbon atoms constituting the benzene ring.
  • the aromatic ring are benzene ring and naphthalene ring.
  • nonaromatic ring examples include cycloalkene rings, of which 5 or 6-membered cycloalkene rings are preferred; rings constituting cyclic ethers, of which those constituting 5 or 6-membered cyclic ethers, such as dihydrofuran ring and dihydropyran ring, are preferred; and lactone rings, of which 5 or 6-membered lactone rings are preferred.
  • Representative examples of the compounds represented by Formula (3) are ortho-xylene, ortho-xylylene glycol, ortho-phthalaldehyde, indan, and tetralin.
  • R 1 , R 2 , R 3 , and R 4 are the same as or different from one another and each represent hydrogen atom, a halogen atom, or an organic group. Two or more of R 1 , R 2 , R 3 , and R 4 may be combined to form an aromatic or nonaromatic ring together with one or more carbon atoms constituting the benzene ring.
  • the halogen atom, organic group, and aromatic or nonaromatic ring are as in Formula (3).
  • ortho-xylene, ortho-xylylene glycol, ortho-phthalaldehyde, indan, or tetralin for example, is used as the compound represented by Formula (3), ortho-phthalic acid, ortho-phthalic acid anhydride (anhydrous ortho-phthalic acid), or a mixture of them is obtained as a main product.
  • the cyclic N-hydroxy- or N-(substituted oxy)-imide compound represented by Formula (5) and derivable from at least one selected from the group consisting of the target product, a reaction intermediate, and a reaction byproduct is used as the catalyst, the catalyst is produced from at least one component selected from the group consisting of the target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction and the produced catalyst is used in the oxidation reaction so as make up for a loss of the catalyst due to denaturation in the reaction.
  • R 1 , R 2 , R 3 , and R 4 are the same as or different from one another and each represent hydrogen atom, a halogen atom, or an organic group. Two or more of R 1 , R 2 , R 3 , and R 4 may be combined to form an aromatic or nonaromatic ring together with one or more carbon atoms constituting the benzene ring. These halogen atom, organic group, and aromatic or nonaromatic ring are as in Formula (3).
  • the substituent R of Formula (5) represents hydrogen atom or an organic group.
  • the organic group is as the organic groups in R of Formula (2).
  • cyclic imide compounds represented by Formula (5) are compounds derivable from ortho-phthalic acid or ortho-phthalic anhydride, including N-hydroxyphthalimide; and N-(substituted oxy)phthalimides such as N-acetoxyphthalimide. These compounds can be advantageously used as the catalyst when, of the compounds represented by Formula (3), ortho-xylene, ortho-xylylene glycol, ortho-phthalaldehyde, indan, or tetralin is used as a raw material.
  • the target product, reaction intermediate, and/or reaction byproduct each formed as a result of the reaction and to be used in production of the catalyst includes a compound represented by Formula (4a), a compound represented by Formula (4b), and a mixture of them, each corresponding to the compound of Formula (3) used as the raw material in the oxidation reaction.
  • ortho-phthalic acid and/or ortho-phthalic anhydride is preferred for the production of the catalyst when, of the compounds of Formula (3), ortho-xylene, ortho-xylylene glycol, ortho-phthalaldehyde, indan, or tetralin is used as the raw material.
  • R k of Formula (3), R k in Formulae (4a) and (4b), and R k of Formula (5), wherein k is 1, 2, 3 or 4, may be the same as or different from one another, as they may change in the course of the oxidation reaction or the production of catalyst.
  • R c , R d , and R e are the same as or different from one another and each represent a group convertible into carboxyl group upon oxidation; and R 5 , R 6 , and R 7 are the same as or different from one another and each represent hydrogen atom, a halogen atom, or an organic group.
  • Two or more of R c , R d , R e , R 5 , R 6 , and R 7 may be combined to form an aromatic or nonaromatic ring together with one or more carbon atoms constituting the benzene ring.
  • the group convertible into carboxyl group upon oxidation is as in the groups convertible into carboxyl group upon oxidation in R a and R b of Formula (3).
  • the halogen atom and organic group are as the halogen atoms and organic groups in R 1 , R 2 , R 3 , and R 4 of Formula (3).
  • the aromatic or nonaromatic ring is as the rings formed by two or more of R a , R b , R 1 , R 2 , R 3 , and R 4 with one or more carbon atoms constituting the benzene ring of Formula (3).
  • Representative examples of the compounds of Formula (6) are 1,2,4-trimethylbenzene, 1,2,4-tris(hydroxymethyl)benzene, and 1,2,4-triformylbenzene.
  • R 5 , R 6 , and R 7 are the same as or different from one another and each represent hydrogen atom, a halogen atom, or an organic group. Two or more of R 5 , R 6 , and R 7 may be combined to form an aromatic or nonaromatic ring together with one or more carbon atoms constituting the benzene ring.
  • the halogen atom, organic group, and aromatic or nonaromatic ring herein are as in Formula (6).
  • 1,2,4-trimethylbenzene, 1,2,4-tris(hydroxymethyl)benzene, and/or 1,2,4-triformylbenzene for example, is used as the compound represented by Formula (6), trimellitic acid, trimellitic anhydride, or a mixture of them is obtained as a main product.
  • a cyclic N-hydroxy- or N-(substituted oxy)-imide compound represented by Formula (8) and derivable from at least one selected from the group consisting of the target product, a reaction intermediate, and a reaction byproduct is used as the catalyst, the catalyst is produced from at least one component selected from the group consisting of the target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction, and the produced catalyst is used in the oxidation reaction so as make up for a loss of the catalyst due to denaturation in the reaction.
  • R 5 , R 6 , and R 7 are the same as or different from one another and each represent hydrogen atom, a halogen atom, or an organic group. Two or more of R 5 , R 6 , and R 7 may be combined to form an aromatic or nonaromatic ring together with one or more carbon atoms constituting the benzene ring. These halogen atom, organic group, and aromatic or nonaromatic ring are as in Formula (6).
  • R of Formula (8) represents hydrogen atom or an organic group.
  • the organic group herein is as the organic groups in R of Formula (2).
  • cyclic imide compounds of Formula (8) are compounds derivable from trimellitic acid or trimellitic anhydride, including 2-carboxy-N-hydroxyphthalimide; and 2-carboxy-N-(substituted oxy)phthalimides such as 2-carboxy-N-acetoxyphthalimide.
  • These compounds can be advantageously used as the catalyst when, of the compounds represented by Formula (6), 1,2,4-trimethylbenzene, 1,2,4-tris(hydroxymethyl)benzene, and/or 1,2,4-triformylbenzene is used as the raw material.
  • the target product, reaction intermediate, and/or reaction byproduct each formed as a result of the reaction to be used in the production of catalyst includes a compound represented by Formula (7a), a compound represented by Formula (7b), and a mixture of them, each corresponding to the compound of Formula (6) used as the raw material.
  • trimellitic acid and/or trimellitic anhydride is preferred for the production of the catalyst when, of the compounds represented by Formula (6), 1,2,4-trimethylbenzene, 1,2,4-tris(hydroxymethyl)benzene, and/or 1,2,4-triformylbenzene is used as the raw material in the oxidation reaction.
  • R p of Formula (6), R p in Formulae (7a) and (7b), and R p of Formula (8), wherein p is 5, 6 or 7, may be the same as or different from one another, since they may change in the course of the oxidation reaction or the production of catalyst.
  • R f , R g , R h , and R i are the same as or different from one another and each represent a group convertible into carboxyl group upon oxidation.
  • R 8 and R 9 are the same as or different from each other and each represent hydrogen atom, a halogen atom, or an organic group. Two or more of R f , R g , R h , R i , R 8 , and R 9 may be combined to form a nonaromatic ring together with one or more carbon atoms constituting the benzene ring.
  • the group convertible into carboxyl group upon oxidation is as the groups convertible into carboxyl group upon oxidation in R a and R b of Formula (3).
  • the halogen atom and organic group are as the halogen atoms and organic groups in R 1 , R 2 , R 3 , and R 4 of Formula (3).
  • the aromatic or nonaromatic ring herein is as the rings formed by two or more of R a , R b , R 1 ,, R 2 , R 3 , and R 9 with one or more carbon atoms constituting the benzene ring, of Formula (3).
  • Representative examples of the compounds of Formula (9) are 1,2,4,5-tetramethylbenzene (durene), 1,2,4,5-tetrakis(hydroxymethyl)benzene, and 1,2,4,5-tetraformylbenzene.
  • R 8 and R 9 are the same as or different from each other and each represent hydrogen atom, a halogen atom, or an organic group.
  • the halogen atom and organic group are as in Formula (9).
  • 1,2,4,5-tetramethylbenzene (durene), 1,2,4,5-tetrakis(hydroxymethyl)benzene, and/or 1,2,4,5-tetraformylbenzene for example, is used as the compound represented by Formula (9), pyromellitic acid, monoanhydrous pyromellitic acid (pyromellitic monoanhydride), dianhydrous pyromellitic acid (pyromellitic dianhydride), or a mixture of them can be obtained as a main product.
  • the cyclic imide compound represented by Formula (11a) and/or the cyclic diimide compound represented by Formula (11b), each derivable from at least one selected from the group consisting of the target product, a reaction intermediate, and a reaction byproduct, is used as the catalyst, the catalyst is produced from at least one component selected from the group consisting of the target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction, and the produced catalyst is used in the oxidation reaction, so as make up for a loss of the catalyst due to denaturation in the reaction.
  • R 8 and R 9 are the same as or different from each other and each represent hydrogen atom, a halogen atom, or an organic group. These halogen atoms and organic groups are as in Formula (9).
  • the substituent R in Formula (11a) represents hydrogen atom or an organic group.
  • the organic groups herein are as the organic groups in R of Formula (2).
  • Representative examples of the cyclic imide compounds of Formula (11a) are compounds derivable from pyromellitic acid and/or pyromellitic monoanhydride, such as N-hydroxypyromellitimide; and N-(substituted oxy)pyromellitimides such as N-acetoxypyromellitimide.
  • Representative examples of the cyclic diimide compounds of Formula (11b) are compounds derivable from pyromellitic acid, pyromellitic monoanhydride, and/or pyromellitic dianhydride, such as N,N'-dihydroxypyromellitic diimide; and N,N'-diacetoxypyromellitic diimide.
  • These compounds can be advantageously used as the catalyst when, of the compounds of Formula (9), 1,2,4,5-tetramethylbenzene (durene), 1,2,4,5-tetrakis(hydroxymethyl)benzene, and/or 1,2,4,5-tetraformylbenzene is used as the raw material in the oxidation reaction.
  • the target product, reaction intermediate, and reaction byproduct, each formed as a result of the reaction, for use in the production of catalyst include a compound represented by Formula (10a), a compound represented by Formula (10b), and a mixture of them, each corresponding to the compound of Formula (9) used as the raw material.
  • At least one selected from the group consisting of pyromellitic acid, pyromellitic monoanhydride, and pyromellitic dianhydride is preferred for the production of the catalyst when, of the compounds represented by Formula (9), 1,2,4,5-tetramethylbenzene (durene), 1,2,4,5-tetrakis(hydroxymethyl)benzene, and/or 1,2,4,5-tetraformylbenzene, for example, is used as the raw material in the oxidation reaction.
  • R q of Formula (9), R q in Formulae (10a), (10b), and (10c), and R q in Formulae (11a) and (11b), wherein q is 8 or 9, may be the same as or different from one another, since they may change in the course of the oxidation reaction or the production of catalyst.
  • the oxygen for use in the oxidation reaction in the present invention can be molecular oxygen.
  • the molecular oxygen can be any of pure oxygen, diluted oxygen with an inert gas such as nitrogen, argon, or helium gas, and the air.
  • One or more promoters can be used in combination with the catalyst N-hydroxy- or N-(substituted oxy)-imide compound in the oxidation reaction.
  • the promoters (co-catalysts) can be any of compounds comprising transition metals or Group 13 elements of the Periodic Table of Elements. Examples of such compounds are oxides, hydroxides, nitrides, oxoacids or salts thereof, oxoacid esters, heteropolyacids or salts thereof, organic acid salts, inorganic acid salts, halides, and complexes. Each of these promoters can be used alone or in combination.
  • transition metal elements are, of the Periodic Table of Elements, Group 3 elements including scandium (Sc), yttrium (Y), as well as lanthanoid elements such as cerium (Ce) and samarium (Sm), and actinoid elements such as actinium (Ac) ; Group 4 elements such as titanium (Ti) and zirconium (Zr); Group 5 elements such as vanadium (V) and niobium (Nb) ; Group 6 elements such as chromium (Cr), molybdenum (Mo), and tungsten (W) ; Group 7 elements such as manganese (Mn), technetium (Tc), and rhenium (Re); Group 8 elements such as iron (Fe) and ruthenium (Ru) ; Group 9 elements such as cobalt (Co) and rhodium (Rh); Group 10 elements such as nickel (Ni), palladium (Pd), and platinum (Pt); and Group 11 elements such as copper (Cu).
  • Preferred elements include Ce, V, Nb, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ni, and Cu.
  • the Group 13 elements include boron (B), and aluminum (Al).
  • Especially preferred promoters (co-catalysts) include divalent or trivalent cobalt compounds such as cobalt acetate and cobalt acetylacetonate; divalent or trivalent manganese compounds such as manganese acetate and manganese acetylacetonate; and zirconium compounds such as zirconium oxoacetate.
  • the amount of the catalyst N-hydroxy- or N-(substituted oxy)-imide compound can be selected within a broad range and is, for example, about 0.0000001 to about 1 mole, preferably about 0.000001 to about 0. 5 mole, more preferably about 0.00001 to about 0.4 mole, and frequently about 0.0001 to about 0.35 mole, per 1 mole of the raw material organic compound (substrate).
  • the amount of the promoter (co-catalyst) is, for example, about 0.001 to about 20 moles, and preferably about 0.005 to about 10 moles, per 1 mole of the catalyst N-hydroxy-or N-(substituted oxy)-imide compound.
  • the amount of the promoter is, for example, about 0.00001 percent by mole to about 10 percent by mole, and preferably about 0.1 percent by mole to about 5 percent by mole, relative to the substrate.
  • the catalyst and the promoter may be supplied to the reaction system in one process, continuously, or intermittently.
  • the reaction temperature in the oxidation reaction can be set according typically to the types of the raw materials, catalyst and promoter, if used, and is, for example, about 0°C to about 300°C, preferably about 30°C to about 250°C, and more preferably about 40°C to about 200°C.
  • the oxidation reaction is generally often carried out at about 40°C to about 150°C.
  • the oxidation reaction can be carried out under atmospheric pressure (normal pressure) or under a pressure (under a load).
  • the reaction can be conducted while adding a dehydrating agent to the oxidation reaction system and/or distilling off by-produced water so as to accelerate the reaction.
  • a dehydrating agent examples include acid anhydrides such as acetic anhydride.
  • the oxidation reaction and dehydration reaction can be carried out stepwise.
  • the target acid anhydride can be formed by forming a carboxylic acid, such as a polycarboxylic acid, upon oxidation reaction, and then conducting a dehydration reaction while adding a dehydrating agent to the reaction system or distilling off by-produced water.
  • the target polyanhydride may be formed by forming a monoanhydride as a result of an oxidation reaction and dehydration reaction, and then repeating the procedure of an oxidation reaction and a dehydration reaction.
  • the "at least one component selected from the group consisting of the target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction" for use as a raw material for the production of catalyst in the present invention also includes such target products, reaction intermediates, and reaction by-products obtained as a result of an oxidation reaction and a subsequent dehydration reaction carried out stepwise as above.
  • the method for producing the catalyst N-hydroxy- or N- (substituted oxy) -imide compound from at least one component selected from the group consisting of the target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction is not specifically limited and can be conducted according to a known synthesis process of imide compounds or using a known reaction.
  • the target products, reaction intermediates, and reaction byproducts for use in the production of catalyst can be highly pure substances that have been highly purified from a reaction mixture but can also be a reaction mixture taken out from an oxidation reactor without purification, or a mixture with another component which can be obtained from the reaction mixture after carrying out a simple separation and purification operation (or device).
  • the catalyst N-hydroxy- or N-(substituted oxy)-imide compound may be produced from at least one component selected from the group consisting of the target compound reaction intermediate, and reaction by-product each formed as a result of the reaction outside the oxidation reaction system as above. Alternatively or in addition, the catalyst may be produced from the at least one component in the oxidation reaction system (in situ).
  • a highly pure catalyst imide compound can be obtained by using part of the target product, since the target product has been highly purified so as to yield a final product.
  • a reaction intermediate or a reaction byproduct is often extracted as a mixture with one or more other components from the reaction mixture (crude reaction mixture).
  • the reaction intermediate is often recycled to the reaction system together with an unreacted raw material, catalyst, solvent, and other reaction intermediates after recovering all or part of the target product and all or part of byproducts from the crude reaction mixture.
  • the mixture of the reaction intermediate, unreacted raw material, catalyst, solvent, and other reaction intermediates is preferably used for the production of catalyst.
  • the mixture may be subjected to a suitable treatment before the production of catalyst.
  • a reaction byproduct is often recovered with other reaction byproducts from the crude reaction mixture.
  • the catalyst imide compound is derived from the reaction byproduct
  • the mixture is preferably used for the production of catalyst.
  • the other components than the reaction byproduct in the mixture include a component that inhibits the catalyst synthesis reaction, the mixture may be subjected to a suitable treatment before the production of catalyst.
  • the target product with one or more reaction intermediates, or the target product with one or more reaction byproducts can be used for the production of catalyst.
  • the target product, reaction intermediate, and reaction byproduct for the production of catalyst are not specifically limited, as long as they can be used in the production of catalyst.
  • Preferred examples of these components for easy reaction are carboxylic acids including monocarboxylic acids such as acetic acid and benzoic acid; dicarboxylic acids such as succinic acid, glutaric acid, ortho-phthalic acid, and terephthalic acid; tricarboxylic acids such as trimellitic acid; tetracarboxylic acids such as pyromellitic acid; corresponding acid anhydrides to these carboxylic acids, of which cyclic acid anhydrides are preferred; and mixtures of them.
  • polycarboxylic acids corresponding polycarboxylic acid anhydrides, and mixtures of them are preferred, and polycarboxylic acids that can form cyclic acid anhydrides, corresponding cyclic acid anhydrides, and mixtures of them are more preferred.
  • a N-hydroxyimide compound can be easily produced by reacting a hydroxylamine with a carboxylic acid (for example, a polycarboxylic acid) or a carboxylic acid anhydride (for example, a polycarboxylic acid anhydride) as the target product, reaction intermediate or reaction byproduct.
  • the hydroxylamine can be free hydroxylamine as, for example, an aqueous solution of hydroxylamine, or a salt of hydroxylamine.
  • the salt of hydroxylamine includes a hydrochloride, a sulfate, and a nitrate.
  • a base is generally used when a hydroxylamine salt is used.
  • Examples of the base are amines such as triethylamine; nitrogen-containing heterocyclic compounds such as pyridine; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; organic acid salts of alkali metals, such as sodium acetate and potassium acetate; ammonia; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; and alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide.
  • amines such as triethylamine
  • nitrogen-containing heterocyclic compounds such as pyridine
  • alkali metal alkoxides such as sodium methoxide and sodium ethoxide
  • organic acid salts of alkali metals such as sodium acetate and potassium acetate
  • ammonia alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such
  • the amount of hydroxylamine or a salt thereof is generally about 1 mole or more (for example, about 1 to about 10 moles), preferably about 1 to about 5 moles, and more preferably about 1 to about 3 moles, per 1 mole of the component to be treated, such as a polycarboxylic acid.
  • the hydroxylamine can be used as a solvent.
  • the reaction temperature is generally about 0°C to about 150°C, and preferably about 5°C to about 120°C.
  • a scavenger for water (a dehydrating agent) may be added to the reaction system.
  • the produced N-hydroxyimide compound can be separated and purified after the completion of the reaction by a conventional separation/purification operation (or device) such as filtration, concentration, extraction, crystallization, or recrystallization.
  • the N-hydroxyimide compound can be subjected to the oxidation reaction as such a purified product or as a mixture with one or more other components, or may be subjected to the oxidation relation after a simple purification operation (or device).
  • the N-(substituted oxy)-imide compound such as a cyclic N-(substituted oxy)-imide compound can be produced from the produced N-hydroxyimide compound, such as a cyclic N-hydroxyimide compound, by a method according to the type of a substituent bound to the oxygen atom.
  • an N-acyloxyimide compound can be produced by reacting a N-hydroxyimide compound with an acid anhydride corresponding to the acyl group or with an acid halide corresponding to the acyl group in the presence of a base.
  • the N-acetoxyimide compound can be produced by reacting a N-hydroxyimide compound with acetic anhydride or with an acetyl halide such as acetyl chloride in the presence of a base such as triethylamine or pyridine.
  • the produced N-(substituted oxy)-imide compound can be separated and purified after the completion of the reaction by a conventional separation/purification operation (or device) such as filtration, concentration, extraction, crystallization, or recrystallization.
  • the N-(substituted oxy)-imide compound can be subjected to the oxidation reaction as such a purified product or as a mixture with one or more other components, or may be subjected to the oxidation relation after a simple purification operation (or device).
  • the N-(substituted oxy) -imide compound such as a cyclic N-(substituted oxy)-imide compound can also be produced by reacting a polycarboxylic acid or a polycarboxylic acid anhydride with a 0-substituted hydroxylamine or a salt thereof.
  • the N-hydroxyimide compound such as a cyclic N-hydroxyimide compound can also be obtained, for example, by subjecting the thus-produced N-(substituted oxy)-imide compound such as a cyclic N-(substituted oxy)-imide compound to hydrolysis to thereby replace the substituent bound to the oxygen atom with hydrogen atom.
  • the production of the catalyst within the oxidation reaction system (in situ) can be carried out, for example, by adding hydroxylamine to the oxidation reaction system.
  • a loss of the catalyst due to denaturation can be easily made up for by effectively using a target product, a reaction intermediate, and/or a reaction byproduct each formed as a result of the reaction.
  • the process for producing an organic compound according to the present invention is based on the oxidation method of an organic compound according to the present invention.
  • the process for producing an organic compound according to the present invention comprises the steps of (A) oxidizing an organic compound with oxygen by the catalysis of at least one N-hydroxy- or N-(substituted oxy)-imide compound derivable from at least one selected from the group consisting of a target product, a reaction intermediate, and a reaction byproduct, (B) separating the target product formed in Step A from at least one component selected from the group consisting of a target product, reaction intermediate, and reaction byproduct each being formed as a result of the reaction and being to be used for producing the catalyst so as to make up for a loss of the catalyst due to denaturation in the reaction, (C) producing a catalyst using the at least one component separated in Step B, and (D) supplying the catalyst produced in Step C to Step A.
  • the process may further comprise the step of (E) recovering an undenaturated catalyst from a reaction mixture and recycling the recovered undenaturated catalyst to Step A, in addition to those steps.
  • Fig. 1 is a schematic process chart of an example of the production process according to the present invention.
  • Reaction Step A an organic compound (a substrate) fed from a line 1 is subjected to an oxidation reaction with oxygen in the presence of a catalyst N-hydroxy- or N-(substituted oxy)-imide compound derivable from a target compound, a reaction intermediate, and/or a reaction byproduct.
  • a reaction apparatus for use in Reaction Step A can comprise, for example, a reactor for oxidizing the substrate; a supplying device for supplying the substrate, the catalyst, and an oxygen-containing gas to the reactor, such as a charging line, a charging pump, and a sparger; a mixing device for admixing the substrate, catalyst, and oxygen-containing gas, such as a stirrer; a device for adjusting the reaction temperature; and a discharging device for discharging a reaction mixture and/or a waste gas from the reactor.
  • the target product and at least one component selected from the group consisting of the target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction are separated from the reaction mixture fed from Reaction Step A via a line 2, which component for the production of catalyst is to be used for producing the catalyst so as to make up for a loss of the catalyst due to denaturation in the reaction.
  • the catalyst (undenaturated catalyst) may be contained in the component for the production of catalyst or may be separated from the component and returned via a line 5 to Reaction Step A (Catalyst Recycling Step E).
  • the separation of the target product from the component for the production of catalyst can be conducted by a separation/purification operation such as filtration, concentration, distillation, extraction, crystallization, or recrystallization, or using a separation device such as a filtering device, a concentrator, a distillator, an extractor, a crystallizer or a recrystallizer.
  • the separated target product is recovered via a line 3, is further purified according to necessity and thereby yields a final product.
  • Part or all of the separated component for the production of catalyst is subjected to Catalyst Production Step C via a line 4, followed by the production of catalyst for make up for a denaturated catalyst.
  • the mixture to be fed to Catalyst Production Step C via the line 4 may contain a denaturated product of the catalyst N-hydroxy- or N-(substituted oxy)-imide compound.
  • An apparatus for producing the catalyst may comprise, for example, a reactor for reacting reaction components; a device for supplying the reaction components to the reactor, such as a charging line and/or a charging pump; a mixing device for admixing the reaction components, such as a stirrer; a device for adjusting the reaction temperature; a device for adjusting pH of the reaction system; a device for exhausting water by-produced in the reaction to outside the system, such as a water-separation device; a device for discharging the reaction mixture from the reactor; and/or a device for separating/purifying the produced catalyst.
  • Catalyst Supplying Step D the catalyst produced in Catalyst Production Step C is supplied via a line 6 to Reaction Step A.
  • Catalyst Recycling Step E the catalyst separated and recovered in Separation Step B (undenaturated catalyst) is recycled via a line 5 to Reaction Step A.
  • the supply of the produced catalyst to Reaction Step A, and the recycling of the undenaturated catalyst to Reaction Step A can be conducted according to a conventional procedure, such as a process of feeding these components to the reactor as intact or after dissolving or suspending them in a suitable solvent or medium.
  • a pump or a belt conveyer for example, can be used.
  • the operations in the steps may be carried out by any system such as a continuous system or batch system. Each step may use one or plural plies of apparatus or equipment, such as a reactor.
  • the liquid layer contained two separated layers, i.e., an upper layer mainly containing cyclohexane, and a lower layer mainly containing acetic acid. Each of these layers was separated and analyzed to find that the conversion from cyclohexane was 17.3% and the selectivities of adipic acid, cyclohexanone, cyclohexanol, and succinic acid were 54.3%, 11.2%, 7.5%, and 4.2%, respectively.
  • the lower layer of the liquid layer was concentrated at 140°C and 100 Torr (13.3 kPa) using an evaporator and thereby yielded 48.1 g of a concentrate.
  • the concentrate was washed with two portions of 40 g of acetic acid.
  • the washed concentrate was 45.4 g in weight. This concentrate contained 10.1 percent by weight of succinic acid, 14.1 percent by weight of glutaric acid, and 72.9 percent by weight of adipic acid.
  • the concentrate was placed in a 300-ml flask and was combined with 30. 2 g of acetic acid.
  • the flask had been equipped with a Dean-Stark fractionating unit, a thermometer, and an agitating blade, and the Dean-Stark fractionating unit had a reflux condenser on an upper portion thereof.
  • the flask was heated on an oil bath, and from the time when acetic acid began distilling, a 50 percent by weight aqueous hydroxylamine solution was fed to the flask at a rate of 0.39 g/hr, and the distillate was extracted at a rate of 11.33 g/hr while feeding acetic acid to the flask so as to keep the liquid level inside the flask.
  • the liquid layer had been separated into two layers, i.e., an upper layer mainly containing cyclohexane, and a lower layer mainly containing acetic acid. Each of these layers was separated and analyzed to find that the conversion from cyclohexane was 17.1%, and the selectivities of adipic acid, cyclohexanone, cyclohexanol, and succinic acid were 53.9%, 12.1%, 7.9%, and 4.6%, respectively.
  • the resulting mixture was combined with 29.2 g of acetic anhydride, and the autoclave was pressurized to 0.5 MPa with nitrogen.
  • the autoclave was held to 120°C on an oil bath to carry out a reaction for one hour, cooled to room temperature, and opened to release the pressure.
  • the mixture was further combined with 1.165 g of N,N'-dihydroxypyromellitic diimide, and the autoclave was pressurized to 4 MPa with a 50:50 (by mole) gaseous mixture of oxygen and nitrogen.
  • the autoclave was held to 150°C on an oil bath to carry out a reaction for three hours, cooled to room temperature, and opened to release the pressure.
  • the reaction mixture was analyzed by high-performance liquid chromatography (HPLC) to find that pyromellitic acid and pyromellitic anhydride were obtained in a total yield of 83%.
  • the mixture in the flask was filtrated to remove precipitates, the filtrate was placed in another flask, concentrated on an oil bath at 150°C, and thereby yielded 31.5 g of a concentrate.
  • the crystals were washed with 5 cc of acetic acid and 5 cc of acetone, subjected to vacuum drying at 130°C for twelve hours, and thereby yielded 7.27 g of crystals.
  • the crystals were analyzed by NMR to find that they contained pyromellitic anhydride and pyromellitic acid in a molar ratio of the former to the latter of 100:7.
  • the crystals were then combined with a solution of 4.82 g of hydroxylamine hydrochloride and 46.6 g of pyridine, and heated at 80°C for fifteen minutes. After cooling, the precipitate was filtrated and washed with 15 g of water.
  • the crystals were combined with 20 g of a 32 percent by weight aqueous acetic acid solution and were stirred at room temperature for thirty minutes.
  • the crystals were filtrated, washed with 7 g of a 9 percent by weight aqueous acetic acid solution, combined with 15 cc of acetone, and stirred at room temperature for two hours.
  • the resulting crystals were filtrated, washed with 5 cc of acetone, dried at 45°C for twelve hours, and thereby yielded 6.68 g of N,N'-dihydroxypyromellitic diimide.

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Claims (9)

  1. Procédé d'oxydation d'un composé organique avec de l'oxygène en présence d'un catalyseur,
    où le catalyseur comprend au moins un composé N-hydroxy- ou N-(substitué)-imide pouvant dériver d'au moins l'un sélectionné dans le groupe constitué d'un produit cible, d'un intermédiaire réactionnel dérivé de matières premières, et d'un sous-produit réactionnel dérivé de matières premières, et
    où le procédé comprend les étapes de :
    production du catalyseur à partir d'au moins un composant sélectionné dans le groupe constitué du produit cible, de l'intermédiaire réactionnel, et du sous-produit réactionnel formés chacun en résultat de la réaction ; et
    utilisation du catalyseur produit dans la réaction d'oxydation,
    où les combinaisons suivantes de composés organiques et de catalyseurs sont utilisées :
    (i) lorsque le composé organique est un cyclo-alcane représenté par la Formule suivante (1) :
    Figure imgb0036
     où « n » représente un nombre entier d'une valeur de 4 à 20, et le cycle montré dans la formule peut être substitué,
    le catalyseur est représenté par la Formule suivante (2) :
    Figure imgb0037
     où « m » représente un nombre entier d'une valeur de 2 à (n-2) ; et R représente un atome d'hydrogène ou un groupe organique, et où le cycle présenté dans la formule peut être substitué, et
    la réaction d'oxydation produit au moins l'un sélectionné dans le groupe constitué d'une cycloalcanone correspondante, d'un cyclo-alcanol correspondant, et d'un acide dicarboxylique correspondant ayant des atomes de carbone au nombre de « n » dans une chaîne principale ;
    (ii) lorsque le composé organique est représenté par la Formule suivante (3) :
    Figure imgb0038
     où Ra et Rb sont identiques ou différents l'un de l'autre et chacun représente un groupe convertible en un groupe carboxyle à l'issue de l'oxydation ; R1, R2, R3, et R4 sont identiques ou différents l'un de l'autre et chacun représente un atome d'hydrogène, un atome d'halogène, ou un groupe organique, où deux ou plusieurs Ra, Rb, R1, R2, R3, et R4 peuvent être combinés pour former un cycle aromatique ou non aromatique conjointement à un ou plusieurs atomes de carbone constituant le cycle benzénique,
    le catalyseur est représenté par la Formule suivante (5) :
    Figure imgb0039
     où R1, R2, R3, et R4 sont identiques ou différents l'un de l'autre et chacun représente un atome d'hydrogène, un atome d'halogène, ou un groupe organique, où deux ou plusieurs de R1, R2, R3, et R4 peuvent être combinés pour former un cycle aromatique ou non aromatique conjointement à un ou plusieurs atomes de carbone constituant le cycle benzénique ; et R représente un atome d'hydrogène ou un groupe organique, et
    la réaction d'oxydation produit au moins l'un sélectionné dans le groupe constitué d'un acide dicarboxylique aromatique représenté par la Formule suivante (4a) et d'un anhydride d'acide dicarboxylique aromatique représenté par la Formule suivante (4b) :
    Figure imgb0040
     où R1, R2, R3, et R4 sont identiques ou différents l'un de l'autre et chacun représente un atome d'hydrogène, un atome d'halogène, ou un groupe organique, où deux ou plusieurs de R1, R2, R3, et R4 peuvent être combinés pour former un cycle aromatique ou non aromatique conjointement à un ou plusieurs atomes de carbone constituant le cycle benzénique ;
    (iii) où le composé organique est représenté par la Formule suivante (6) :
    Figure imgb0041
     où Rc, Rd, et Re sont identiques ou différents l'un de l'autre et chacun représente un groupe convertible en groupe carboxyle à l'issue de l'oxydation ; et R5, R6, et R7 sont identiques ou différents l'un de l'autre et chacun représente un atome d'hydrogène, un atome d'halogène, ou un groupe organique, où deux ou plusieurs de Rc, Rd, Re, R5, R6, et R7 peuvent être combinés pour former un cycle aromatique ou non aromatique conjointement à un ou plusieurs atomes de carbone constituant le cycle benzénique,
    le catalyseur est représenté par la Formule suivante (8) :
    Figure imgb0042
     où R5, R6, et R7 sont identiques ou différents l'un de l'autre et chacun représente un atome d'hydrogène, un atome d'halogène, ou un groupe organique, où deux ou plusieurs de R5, R6, et R7 peuvent être combinés pour former un cycle aromatique ou non aromatique conjointement à un ou plusieurs atomes de carbone constituant le cycle benzénique ; et R représente un atome d'hydrogène ou un groupe organique, et
    la réaction d'oxydation produit au moins l'un d'un acide tricarboxylique aromatique représenté par la Formule suivante (7a) et d'un monoanhydride d'acide tricarboxylique aromatique représenté par la Formule suivante (7b) :
    Figure imgb0043
     où R5, R6, et R7 sont identiques ou différents l'un de l'autre et chacun représente un atome d'hydrogène, un atome d'halogène, ou un groupe organique, où deux ou plusieurs de R5, R6, et R7 peuvent être combinés pour former un cycle aromatique ou non aromatique conjointement à un ou plusieurs atomes de carbone constituant le cycle benzénique ;
    ou
    (iv) lorsque le composé organique est représenté par la Formule suivante (9) :
    Figure imgb0044
     où Rf, Rg, Rh et Ri sont identiques ou différents l'un de l'autre et chacun représente un groupe convertible en groupe carboxyle à l'issue de l'oxydation ; et R8 et R9 sont identiques ou différents l'un de l'autre et chacun représente un atome d'hydrogène, un atome d'halogène, ou un groupe organique, où deux ou plusieurs de Rf, Rg, Rh, Ri, R8, et R9 peuvent être combinés pour former un cycle non aromatique conjointement à un ou plusieurs atomes de carbone constituant le cycle benzénique,
    le catalyseur est un composé imide cyclique représenté par la Formule suivante (11a) ou un composé diimide cyclique représenté par la Formule suivante (11b) :
    Figure imgb0045
     où R8 et R9 sont identiques ou différents l'un de l'autre et chacun représente un atome d'hydrogène, un atome d'halogène, ou un groupe organique ; et R représente un atome d'hydrogène ou un groupe organique, et
    la réaction d'oxydation produit au moins l'un sélectionné dans le groupe constitué d'un acide tétracarboxylique aromatique représenté par la Formule suivante (10a), d'un monoanhydride d'acide tétracarboxylique aromatique représenté par la Formule suivante (10b), et d'un dianhydride d'acide tétracarboxylique aromatique représenté par la Formule suivante (10c) :
    Figure imgb0046
     où R8 et R9 sont identiques ou différents l'un de l'autre et chacun représente un atome d'hydrogène, un atome d'halogène, ou un groupe organique.
  2. Procédé selon la revendication 1, où le composé organique est un cyclo-alcane représenté par la Formule (1), le catalyseur est représenté par la Formule (2), et le procédé comprend l'oxydation du cyclohexane avec de l'oxygène pour produire de là au moins l'un sélectionné dans le groupe constitué de la cyclohexanone, du cyclohexanol, et de l'acide adipique,
    où le catalyseur comprend au moins l'un sélectionné dans le groupe constitué du N-hydroxy- ou N-(oxy substitué)-succinimide et du N-hydroxy- ou N-(oxy substitué)-glutarimide dérivés de l'acide succinique et de l'acide glutarique, respectivement, chacun comme sous-produit réactionnel, et
    où le procédé comprend les étapes de :
    production du catalyseur à partir de l'acide succinique et/ou de l'acide glutarique formés en résultat de la réaction ; et
    utilisation du catalyseur produit dans la réaction d'oxydation.
  3. Procédé selon la revendication 1, où le composé organique est un cyclo-alcane représenté par la Formule (1), le catalyseur est représenté par la Formule (2), et le procédé comprend l'oxydation du cyclopentane avec de l'oxygène pour produire de là au moins l'un sélectionné dans le groupe constitué de la cyclopentanone, du cyclopentanol, et de l'acide glutarique,
    où le catalyseur comprend au moins l'un sélectionné dans le groupe constitué du N-hydroxy- ou N-(oxy substitué)-succinimide dérivé de l'acide succinique comme sous-produit réactionnel, et du N-hydroxy- ou N-(oxy substitué)-glutarimide dérivé de l'acide glutarique comme produit cible, et
    où le procédé comprend les étapes de :
    production du catalyseur à partir de l'acide succinique et/ou de l'acide glutarique formés en résultat de la réaction ; et
    utilisation du catalyseur produit dans la réaction d'oxydation.
  4. Procédé selon la revendication 1, où le composé organique est un cyclo-alcane représenté par la Formule (1), le catalyseur est représenté par la Formule (2), et le procédé comprend l'oxydation du cyclododécane avec de l'oxygène pour produire de là au moins l'un sélectionné dans le groupe constitué de la cyclododécanone, du cyclododécanol, et de l'acide dodécanedioïque,
    où le catalyseur comprend au moins l'un sélectionné dans le groupe constitué du N-hydroxy- ou N-(oxy substitué)-succinimide, et du N-hydroxy- ou N-(oxy substitué)-glutarimide dérivés de l'acide succinique et de l'acide glutarique, respectivement, comme sous-produits réactionnels, et
    où le procédé comprend les étapes de :
    production du catalyseur à partir de l'acide succinique et/ou de l'acide glutarique formés en résultat de la réaction ; et
    utilisation du catalyseur produit dans la réaction d'oxydation.
  5. Procédé selon la revendication 1, où le composé organique est représenté par la Formule (3), le catalyseur est représenté par la Formule (5), et le procédé comprend en outre les étapes de :
    production du catalyseur à partir d'au moins un composant sélectionné dans le groupe constitué de l'acide dicarboxylique aromatique représenté par la Formule (4a) et de l'anhydride d'acide dicarboxylique aromatique représenté par la Formule (4b) chacun formé en résultat de la réaction ; et
    utilisation du catalyseur produit dans la réaction d'oxydation.
  6. Procédé selon la revendication 1, où le composé organique est représenté par la Formule (6), le catalyseur est représenté par la Formule (8), et le procédé comprend en outre les étapes de :
    production du catalyseur à partir d'au moins un composant sélectionné dans le groupe constitué d'un acide tricarboxylique aromatique représenté par la Formule (7a) et d'un monoanhydride d'acide tricarboxylique aromatique représenté par la Formule (7b) chacun formé en résultat de la réaction ; et
    utilisation du catalyseur produit dans la réaction d'oxydation.
  7. Procédé selon la revendication 1, où le composé organique est représenté par la Formule (9), le catalyseur est un composé imide cyclique représenté par la Formule (11a) ou un composé diimide cyclique représenté par la Formule (11b), et le procédé comprend en outre les étapes de :
    production du catalyseur à partir d'au moins un composant sélectionné dans le groupe constitué de l'acide tétracarboxylique aromatique représenté par la Formule (10a), du monoanhydride d'acide tétracarboxylique aromatique représenté par la Formule (10b), et du dianhydride d'acide tétracarboxylique aromatique représenté par la Formule (10c), chacun formé en résultat de la réaction ; et
    utilisation du catalyseur produit dans la réaction d'oxydation.
  8. Procédé selon la revendication 1 comprenant les étapes de :
    (A) oxydation du composé organique avec de l'oxygène par la catalyse du au moins un composé N-hydroxy- ou N-(oxy substitué)-imide ;
    (B) séparation du produit cible formé à l'étape A du au moins un composant sélectionné dans le groupe constitué d'un produit cible, d'un intermédiaire réactionnel, et d'un sous-produit réactionnel formés chacun en résultat de la réaction et devant être utilisés pour la production du catalyseur ;
    (C) production d'un catalyseur en utilisant le au moins un composant séparé dans l'étape B ; et
    (D) alimentation du catalyseur produit dans l'étape C au niveau de l'étape A.
  9. Procédé selon la revendication 8 comprenant en outre l'étape de (E) récupération d'un catalyseur non dénaturé d'un mélange réactionnel et recyclage du catalyseur non dénaturé récupéré au niveau de l'étape A.
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JP2001288122A (ja) 2000-04-04 2001-10-16 Daicel Chem Ind Ltd 反応生成物と触媒との分離方法
US6555004B2 (en) 2000-05-02 2003-04-29 Sumitomo Chemical Company, Limited Method for separating catalyst, product and solvent
JP2002020331A (ja) 2000-05-02 2002-01-23 Sumitomo Chem Co Ltd 触媒、生成物及び反応溶媒の分離方法
TWI294308B (fr) * 2000-11-15 2008-03-11 Daicel Chem

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CA2597120A1 (fr) 2006-09-14
EP1862442A1 (fr) 2007-12-05
CN101137606B (zh) 2012-07-25
KR101280135B1 (ko) 2013-06-28
US7910749B2 (en) 2011-03-22
TWI374774B (en) 2012-10-21
KR20070110421A (ko) 2007-11-16
CN101137606A (zh) 2008-03-05
JP4942645B2 (ja) 2012-05-30
JPWO2006095568A1 (ja) 2008-08-14
US20080269507A1 (en) 2008-10-30
EP1862442A4 (fr) 2010-06-02
TW200642759A (en) 2006-12-16
CA2597120C (fr) 2013-08-06

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